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Nicola Marzari

Publications and source records attributed to Nicola Marzari.

At least 19 recordsLinked to original sources
arXiv2026

Assessing the magnetic states and the accuracy of first-principles Hubbard corrections for the battery cathode Li$_x$CoO$_2$ ($x=0,1$)

Li$_x$CoO$_2$ is a prototypical layered cathode material for Li-ion batteries, yet its accurate description from first principles remains challenging because of self-interaction errors, weak interlayer interactions, and a complex magnetic energy landscape. Here, we present a systematic investigation of the structural, electronic, magnetic, and electrochemical properties of Li$_x$CoO$_2$ ($x=0,1$) using density-functional theory augmented with self-consistent Hubbard corrections and long-range van der Waals interactions, together with a systematic exploration of possible magnetic states. The on-site interactions on Co-$3d$ and O-$2p$ states, as well as inter-site Co-O interactions, are determined from first principles using linear-response theory in the framework of density-functional perturbation theory, with Löwdin-orthogonalized atomic orbitals employed as Hubbard projectors. For LiCoO$_2$, the inclusion of Hubbard corrections provides an accurate description of the structural properties, while the electronic structure is very sensitive to the choice of Hubbard projectors. In particular, frontier Wannier-function projectors substantially improve the description of the occupied electronic states compared with localized atomic orbitals. For CoO$_2$, we demonstrate that a systematic exploration of the magnetic energy landscape is essential to identify the lowest-energy low-spin ground state. However, the resulting Hubbard-corrected electronic structure is insulating, consistent with the prediction of the HSE06 hybrid functional, but in contrast to the experimentally observed metallic behavior. Structural relaxation further drives the system toward a different metallic solution with an electronic configuration inconsistent with low-spin Co$^{4+}$ character. Despite these limitations, the calculated intercalation voltages agree well with experiment, with deviations as small as 2%.

cond-mat.mtrl-sci↗
arXiv2026

DFT+U+V is equivalent to DFT+U with density-dependent hybridized projectors

Hubbard-corrected density-functional theory (DFT+$U$) is a popular tool for first-principles modeling of materials with localized $d$ or $f$ electrons, but its on-site corrections tend to over-localize charge and break covalent bonds. Inter-site $+V$ corrections were introduced to counter this and are now widely used, but a formal justification has been lacking. Here we show that -- to first order in $V/U$ -- inter-site corrections are exactly equivalent to on-site DFT+$U$ evaluated on a density-matrix-dependent redefinition of the Hubbard projectors, hybridized with those of neighboring sites, providing insight into the explicit mechanism by which $V$ affects covalency. If the projectors are held frozen, as is common practice, the equivalence partially breaks down. Beyond reinterpreting the formalism, these results sharpen the questions of how $V$ should be computed and what the Hubbard subspaces fundamentally are.

cond-mat.mtrl-sci↗
arXiv2026

Randomized Block Davidson Eigensolvers for Plane-Wave Density-Functional Theory

Iterative diagonalization is the dominant cost of plane-wave density-functional theory (DFT), with search-space orthogonalization scaling particularly quickly with problem size and the number of target states. We present a randomized block Davidson-type eigensolver that replaces Euclidean orthogonalization with randomized Gram-Schmidt in a sketched inner product, requiring only a single pass over the basis while keeping its conditioning bounded independently of the input vectors. This modification changes only the Rayleigh-Ritz step, which becomes a definite generalized Hermitian eigenproblem. Ritz extraction remains exact, preserving true Ritz pairs and the interlacing property that makes each band energy an upper bound on the true one. The method is implemented in mixed precision for CPUs and GPUs from a single Julia code, interfaces matrix-free with DFTK, and is released in the open-source RandESC library. On sparse test problems with a fixed number of eigenpairs, the sketched solver overtakes its deterministic counterpart beyond matrix dimensions of about $2\times 10^4$ and is $25\%$ faster at $5\times 10^5$. In full self-consistent field DFT calculations, however, both Davidson variants outperform the locally optimal block preconditioned conjugate gradient (LOBPCG) reference only by $5$ to $11\%$ in total time, while the additional benefit of sketching is limited. As the number of requested states grows with system size, orthogonalization savings are offset by the generalized eigenproblem. Therefore, the regime in which sketching pays off is set by how the number of wanted states scales with the problem dimension, not by the eigensolver as such.

math.NA↗
arXiv2026

Thermal transport in crystals: from the quantum Dyson equation to mesoscopic phonon hydrodynamics

Thermal transport in dielectric, non-magnetic crystals is mediated by quantized lattice vibrations, which drift and interact when driven out of equilibrium by a temperature gradient. This phenomenon can be described at multiple theoretical levels, ranging from fully quantum descriptions to semiclassical and mesoscopic continuum approaches. This review rigorously discusses the theoretical steps and approximations connecting these levels, bridging quantum phonon Dyson and Kadanoff-Baym equations and semiclassical Boltzmann transport formalism, and discussing the coarse-graining procedures that yield mesoscopic viscous heat equations for non-diffusive, hydrodynamic heat transport in devices. We show how the Guyer-Krumhansl and dual-phase-lag equations emerge as special linear-isotropic-band and inviscid limits of the viscous heat equations, respectively; most importantly, we demonstrate that these equations predict not only Poiseuille flow and second sound, but also more exotic effects such as negative thermal resistance, steady-state thermal backflow and vortices. We highlight how combining these frameworks with first-principles simulations connects microscopic phonon physics to observable non-diffusive heat-transport phenomena and guides their detection, amplification, and control. We recast the viscous heat equations in terms of Helmholtz and biharmonic equations solved analytically, and use this to discuss similarities and differences between the macroscopic behavior of the phonon fluid and other hydrodynamic systems, such as classical and electron fluids, focusing on compressibility, vorticity, and their influence on phonon hydrodynamics. We conclude with a roadmap to generalize the tools used to describe phonon hydrodynamics to other quasiparticles, motivating future advances in collective quantum transport phenomena in solids.

cond-mat.mtrl-sci↗
arXiv2026

First-principles screening of materials with extreme effective masses

The effective mass of charge carriers is a fundamental descriptor of the electronic structure of materials, and can be used to assess performance in electronics applications, or to screen for thermoelectrics and transparent conductors. Here, we perform a high-throughput computational screening of approximately 20,000 experimentally known three-dimensional stoichiometric inorganics obtained from the Materials Cloud 3D structure database. By combining density-functional theory calculations and maximally localized Wannier functions, we are able to compute the full conductivity effective mass tensor for electrons and holes from the Boltzmann transport equation in the constant relaxation-time approximation. This approach captures the effects of band non-parabolicity, anisotropy, and valley multiplicity that would be neglected by standard parabolic fittings. The screening identifies a curated set of candidates exhibiting extreme electronic properties, from ultra-low to ultra-large effective masses, these latter associated with flat-band physics. We validate the workflow by recovering established high-mobility semiconductors and highlight promising novel candidates. Furthermore, we classify materials by their mass anisotropy and discuss the physical limits of defining a conductivity effective mass in narrow-gap regimes at room temperature. Importantly, the resulting dataset provides a systematic roadmap to search for high-performance materials in novel chemical spaces.

cond-mat.mtrl-sci↗
arXiv2026

Resonant Raman spectroscopies beyond density-functional theory

Resonant Raman spectroscopy probes, in a single measurement, how electrons and phonons couple in a material. Density-functional theory (DFT) typically reproduces well phonon frequencies, but resonant Raman intensities hinge on electron-phonon matrix elements and electronic transitions that are far more sensitive to the underlying exchange-correlation approximation. However, electron-phonon coupling has so far been accessible only through linear-response theories developed for a handful of semilocal DFT methods, leaving the sensitivity of resonant Raman intensities to the electronic-structure approximation essentially unexplored. Here, we introduce a general finite-difference framework that can compute resonant Raman tensors for any electronic-structure method capable of delivering forces, eigenvalues, and wavefunctions of pristine and displaced configurations. We apply the formalism to graphene and monolayer MoS$_2$, using hybrid functionals or meta-GGAs, and show that these approaches systematically enhance electron-phonon couplings relative to semilocal DFT, reflecting reduced dielectric overscreening. A decomposition of the Raman tensor shows that accurate intensities require electronic eigenvalues and electron-phonon matrix elements to be treated consistently at the same level of theory. Among the approaches tested, hybrid functionals provide the best overall agreement with experiment. Because the framework needs only quantities every electronic-structure code already produces, it opens the door to systematic, beyond-DFT Raman characterization or benchmarking against experiments, especially for 2D materials.

cond-mat.mtrl-sci↗
arXiv2026

Strong correlations and local self-energies from on-site ensembles

Addressing the many-body electronic-structure problem is a central goal of modern condensed-matter physics. Paramagnetic Mott insulators, in particular, have long represented a challenge for standard approaches, such as density-functional theory. Historically, these systems have been tackled either by considering many-body dynamics, as in the case of dynamical mean-field theory (DMFT), or, more recently, by invoking a polymorphous description consisting of large supercells populated with static symmetry-broken motifs whose spatial average restores the paramagnetic state. Inspired by these viewpoints, we introduce the on-site dephased ensemble (DE) approximation, in which the local electronic-structure problem is described by a thermal ensemble of all accessible local static solutions; this gives rise to a strong frequency dependence of the local electronic self-energy, as seen in DMFT or in the coherent-potential approximation of disordered alloys. We show that the DE successfully recovers defining hallmarks of strongly correlated Mott systems, both in terms of the self-energy as well as the persistence of local moments in time, in quantitative agreement with DMFT. By bypassing expensive quantum Monte Carlo solvers or large supercell calculations, this approach offers efficient routes to treating paramagnetic Mott systems in a first-principles setting, and highlights a deeper connection between the physics of strong correlations and that of disorder.

cond-mat.str-el↗
arXiv2026

Ultrafast magnetization induced by linearly polarized pulses is widespread in nonmagnetic semiconductors

Ultrafast optical on-off switching of magnetic order promises near-petahertz information processing. Recently, it has been proposed that non-magnetic semiconductors with narrow band edges or strong exchange interactions could display ultrafast magnetization when photoexcited with linearly polarized femtoseconds pulses, but the experimental detection of this effect remains a challenge, mostly for the lack of suitable candidate compounds. Here, we present a high-throughput first-principles screening of the MC3D database of experimentally known inorganic crystals, identifying nearly 440 non-magnetic semiconductors that develop spin polarization under photoexcitation with linearly polarized pulses via a light-induced exchange-driven instability. We determine how the crystal field environment and band-edge orbital character govern the magnitude and the type of magnetic order of the photoinduced state and we unveil systematic chemical and periodic trends that provide intuitive guidance for materials selection. Our results argue that on-off switching of magnetization with linearly polarized femtosecond pulses is a widespread occurrence in non-magnetic semiconductors, opening novel avenues for experimental verification and application.

cond-mat.mtrl-sci↗
arXiv2026

Quantum annealing for materials

Finding the global minimum of a potential energy surface is a fundamental challenge in materials science, with applications ranging from protein folding to cluster physics and, more broadly, to systems in which the number of (meta)stable configurations grows prohibitively large. In recent decades, quantum annealing (QA) has emerged as a promising global optimization strategy, exploiting quantum fluctuations in contrast to the thermal fluctuations that drive its classical counterpart. Here, we introduce a novel implementation of QA based on path-integral molecular dynamics, an efficient and well-established framework for sampling the quantum nuclear density without the need to manipulate many-body wavefunctions explicitly. While retaining the flexibility and simplicity of molecular dynamics simulations, this quantum-annealing protocol delivers strong performance across a wide range of atomic systems, simulated by either empirical force fields or machine-learning interatomic potentials. The method can be used either as a global optimizer of the potential-energy surface, or as a quantum-informed structure-search strategy in which nuclear quantum effects are included directly in the optimization workflow -- a feature particularly relevant for materials such as high-pressure hydrides.

cond-mat.mtrl-sci↗
arXiv2026

Accelerating discovery across scientific disciplines through reproducible workflows with AiiDAlab

With ever-increasing computational capabilities, robust and automated research workflows have become essential for orchestrating large numbers of interdependent simulations. However, significant technical expertise is still required to configure execution environments, define calculation inputs, interpret outputs, and manage the complexity of parallel code execution on remote machines. To address these challenges, we developed AiiDAlab, a Jupyter-based web platform powered by the AiiDA computational infrastructure that provides a framework for managing and automating computational workflows while ensuring reproducibility through full provenance tracking. Through a collection of open-source user-friendly applications, AiiDAlab enables scientists to set up, execute, and analyze complex computational workflows without interacting directly with the underlying technical details, allowing them to focus on their research questions. In this paper, we discuss how AiiDAlab has matured over the past few years, expanding beyond computational materials science and its AiiDA origins. We present recent developments towards integrating with electronic laboratory notebooks (ELNs) for FAIR-compliant data management, adoption in large-scale facilities for secure access to experimental data and analytical tools, and applications in educational settings. Together with community-driven efforts to simplify onboarding, improve access to computational resources, and support large-scale data workflows, these advancements position AiiDAlab as a powerful platform for accelerating scientific discovery and fostering collaboration across disciplines.

cs.DC↗
arXiv2026

optimade-maker: Automated generation of interoperable materials APIs from static datasets

Atomistic structural data are central to materials science, condensed matter physics, and chemistry, and are increasingly digitised across diverse repositories and databases. Interoperable access to these heterogeneous data sources enables reusable clients and tools, and is essential for cross-database analyses and data-driven materials discovery. Toward this aim, the OPTIMADE (Open Databases Integration for Materials Design) specification defines a standard REST API for atomistic structures and related properties. However, deploying and maintaining compliant services remains technically demanding and poses a significant barrier for many data providers. Here, we present optimade-maker, a lightweight toolkit for the automated generation of OPTIMADE-compliant APIs directly from raw atomistic structure and property data. The toolkit supports a wide range of raw datasets, enables conversion to a standardised OPTIMADE data representation, and allows for rapid deployment of APIs in both local and production environments. We further demonstrate it through an automated service on the Materials Cloud Archive, which automatically creates and publishes OPTIMADE APIs for contributed datasets, enabling immediate discoverability and interoperability. In addition, we implement data transformation pipelines for the Cambridge Structural Database (CSD) and the Inorganic Crystal Structure Database (ICSD), enabling unified access to these curated resources through the OPTIMADE framework. By lowering the technical barriers to interoperable data publication, optimade-maker represents an important step toward a scalable, FAIR materials data ecosystem integrating both community-contributed and curated databases.

cs.DB↗
arXiv2026

Dynamical pseudopotentials

Pseudopotential theory has greatly driven first-principles calculations in materials, replacing the explicit treatment of the chemically inert core electrons with an effective potential acting only on the valence states. This is inherently an embedding problem, where tracing out the core electrons can be formulated in terms of a dynamical embedding potential. Motivated by this perspective, we first introduce a framework for dynamical (i.e., energy-dependent) pseudopotentials, showing how this leads to generalized norm-conservation conditions. Then, adopting a sum-over-poles representation, we disentangle the number of reference energies from the number of projectors; this allows to reproduce all-electron scattering at many reference energies with great accuracy and over very extended energy ranges. We further show that these pseudopotentials enter naturally into many-body total energy functionals, leading for the first time to a consistent and unified treatment of the all-electron atom, the pseudo-atom, and the solid within the same electronic-structure theory.

cond-mat.mtrl-sci↗
arXiv2026

Rashba engineering at van der Waals interfaces

Two-dimensional transition metal dichalcogenide (TMD) interfaces offer a versatile platform for studying emergent quantum phenomena and enabling novel device functionalities. When distinct TMD monolayers are stacked vertically or laterally stitched, their interfaces can exhibit unique electronic band alignments, giving rise to long-lived interlayer excitons, charge transfer effects, and moiré superlattices with correlated states. Here, we demonstrate that the interface between a large variety of two different epitaxially grown TMD monolayers controls the intensity and sign of the Rashba spin splitting, which is probed using THz spintronic emission. Optimized TMD heterobilayers, such as HfSe$_2$/PtSe$_2$, show enhanced THz emission that surpass the spin-to-charge conversion efficiency of bulk TMDs, confirming the presence of Rashba states with large spin splitting at the interface. By combining spin- and angle-resolved photoemission spectroscopy with density functional theory, we reveal that the electronic hybridization between the two different TMD monolayers gives rise to extended in-gap states with strong Rashba spin-orbit coupling. The choice of TMD layers enables to engineer the sign and strength of spin-to-charge conversion in van der Waals heterobilayers opening up perspectives to build efficient and tunable THz spintronic emitters.

cond-mat.mes-hall↗
arXiv2026

Extraction of the self energy and Eliashberg function from angle resolved photoemission spectroscopy using the xARPES code

Angle-resolved photoemission spectroscopy is a powerful experimental technique for studying anisotropic many-body interactions through the electron spectral function. Existing attempts to decompose the spectral function into non-interacting dispersions and electron-phonon, electron-electron, and electron-impurity self-energies rely on linearization of the bands and manual assignment of self-energy magnitudes. Here, we show how self-energies can be extracted consistently for curved dispersions. We extend the maximum-entropy method to Eliashberg-function extraction with Bayesian inference, optimizing the parameters describing the dispersions and the magnitudes of electron-electron and electron-impurity interactions. We compare these novel methodologies with state-of-the-art approaches on model data, then demonstrate their applicability with two high-quality experimental data sets. With the first set, we identify the phonon modes of a two-dimensional electron liquid on TiO$_2$-terminated SrTiO$_3$. With the second set, we obtain unprecedented agreement between two Eliashberg functions of Li-doped graphene extracted from separate dispersions. We release these functionalities in the novel Python code xARPES.

cond-mat.mtrl-sci↗
arXiv2026

Predicting challenging phase transitions with Bayesian active learning

Materials underpin modern technologies, from energy harvesting, storage, and conversion to information and communication technologies. Their functionality is often governed by the interplay between competing phases, as thermodynamic behavior shapes microscopic properties and ultimately determines technological performance; for instance, the light absorption of inorganic metal-halide perovskites in solar cells. Accurately predicting crystal thermodynamics, however, remains a major challenge for computational approaches because strong anharmonic effects require extensive sampling of the potential energy surface. Here, we present an on-the-fly Bayesian framework, combined with the stochastic self-consistent harmonic approximation, for learning first-principles interatomic potentials. This approach enables the prediction of thermodynamic properties over a broad temperature range with first-principles accuracy while requiring training on only a few tens to a few hundreds of atomic configurations. To demonstrate its power, we investigate the thermodynamic and dynamical properties of Li$_2$O, $α$-CsPbI$_3$, and $δ$-CsPbI$_3$, requiring only 44, 256, and 50 total-energy calculations, respectively. Notably, we show that this framework accurately captures the phase diagram of CsPbI$_3$, which explains its spontaneous degradation into the non-absorbing yellow phase, predicting the transition temperature with remarkable accuracy and efficiency. More broadly, the method presented opens a novel route toward accelerated materials engineering under realistic conditions for a wide range of technologically relevant applications, including solid-state batteries, optoelectronic devices, and memristors.

cond-mat.mtrl-sci↗
arXiv2026

Probing the real-space density of spin-entangled electrons

On the textbook example of an isolated antiferromagnetic Heisenberg dimer, we demonstrate that the magnetic form factor and the magnetic electron density distribution can be extracted from the momentum-dependence of the inelastic neutron scattering (INS) intensity of a magnetic excitation. We measure the three-dimensional (3D) magnetic structure factor of the singlet-to-triplet excitation in Cu(II) acetate monohydrate with INS. Using a minimal parametrization of the magnetic electron density, we deduce the real-space density of the spin-entangled electrons and the transfer of magnetic electron density between metal and ligand atoms from the experimental data. Density functional theory (DFT) calculations reproduce the measured structure factor quantitatively, providing a direct validation of DFT broken-symmetry spin densities against full 3D INS data. The quantitative agreement between experiment, parametrization, and theory establishes a robust framework for determining magnetic form factors and the magnetic electron density in a broad range of magnetic materials and demonstrates INS as a probe of the envelope of spatial electronic wavefunctions.

cond-mat.str-el↗
arXiv2026

Predicting the suitability of photocatalysts for water splitting using Koopmans spectral functionals: The case of TiO$_2$ polymorphs

Photocatalytic water splitting has attracted considerable attention for renewable energy production. Since the first reported photocatalytic water splitting by titanium dioxide, this material remains one of the most promising photocatalysts, due to its suitable band gap and band-edge positions. However, predicting both of these properties is a challenging task for existing computational methods. Here we show how Koopmans spectral functionals can accurately predict the band structure and level alignment of rutile, anatase, and brookite TiO$_2$ using a computationally efficient workflow that only requires (a) a DFT calculation of the photocatalyst/vacuum interface and (b) a Koopmans spectral functional calculation of the bulk photocatalyst. The success of this approach for TiO$_2$ suggests that this strategy could be deployed for assessing the suitability of novel photocatalyst candidates.

cond-mat.mtrl-sci↗
arXiv2026

Direct observation of strain and confinement shaping the hole subbands of Ge quantum wells

Germanium-silicon-germanium (Ge/Si$_{x}$Ge$_{1-x}$) heterostructures have emerged as a promising platform for hole-spin quantum technologies and high-mobility electronics, where strain and quantum confinement strongly reshape the Ge valence bands. However, the momentum-resolved valence-band structure of buried strained Ge quantum wells has so far been inferred only indirectly. Here we use soft X-ray angle-resolved photoemission spectroscopy (SX-ARPES) to directly probe the electronic structure of strained Ge quantum wells embedded in SiGe barriers. We resolve strain-split and size-quantized valence subbands, determine their heavy-hole, light-hole and split-off composition, and measure the valence-band offset at the Ge/SiGe heterojunction. Comparison with ab initio calculations shows that an accurate description requires explicit inclusion of the confinement potential imposed by the SiGe barrier, which plays a decisive role in determining the dispersion, ordering and mixing of the hole states. Our results provide the first direct experimental picture of how strain and confinement determine the valence-band structure of Ge quantum wells, establishing a foundation for predictive modelling of hole-spin qubits and high-mobility devices based on group-IV heterostructures.

cond-mat.mtrl-sci↗